Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
  • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
  • B29C41/20—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. moulding inserts or for coating articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/10—Processes of additive manufacturing
  • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2009/00—Layered products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing

Definitions

• the present invention relates to direction-independent impact-resistant 3-D plastic moldings with a scratch-resistant and solvent-resistant surface and film insert molding process for their preparation.
• the film insert molding technology has become established. It provides that the front surface of a part is first prefabricated from a coated film two- or three-dimensional and then filled or back-injected with a plastic melt from the back.
• the front side is sufficiently protected against chemical and mechanical effects. This is often achieved in the prior art by a corresponding coating or coating of the surface.
• a coating or coating should already be applied to the film, which then passes through the film with all further forming steps and then finally cured, e.g. by UV exposure.
• plastic parts used widely in the car in any other means of transportation, electrical and electronic equipment and in the construction industry their impact and impact resistance up to low application-relevant temperatures of up to - 30 ° C high demands.
• products made of polycarbonate have this property.
• polycarbonate surfaces also have some sensitivity to scratches and solvents.
• brittle or less impact-resistant polymer layers applied to polycarbonate for example paints for increasing the scratch resistance or PMMA cover layers, adversely affect the impact strength of polycarbonate.
• Plastic parts made of coextruded PC / PMMA films therefore generally show no acceptable impact resistance, especially when the impact comes from the side of the polycarbonate, that is, the polymethyl methacrylate is in the tensile zone of the joint.
• the coating agent of the present invention can be easily and efficiently obtained.
• coatings obtainable with it on many surfaces, in particular for the films insert molding process in the eligible films are sufficiently block-resistant, but then can thermally deform arbitrarily together with the coated substrate and get after curing such as UV radiation scratch-resistant and solvent-resistant surface.
• a direction-independent impact resistance of the shaped body is obtained when the surface coating of the film is present in a thickness in the range of ⁇ 0.1 microns to ⁇ 20 microns.
• Tough is defined in the sense of the puncture test on the nature of the fracture thereby generated, namely by the distinction in breaking and brittle fracture, as will be explained below:
• the penetration test based on DIN EN ISO 6603-1 is with a fall mass of 13 kg, a sample size of 50x50 mm 2 , a mandrel diameter of 20 mm and a round support with 40 mm hole diameter performed, the impact velocity for determining the toughened / brittle transition is varied.
• the type of fracture can be determined from the fracture pattern of the beaten specimens.
• a fracture fracture is both plastic deformation without cracking (according to standard) and (deviating from the standard) piercing of the specimen, if it is in a piece remains.
• breaking the sample into two or more pieces is considered.
• the scratch resistance can be determined from the pencil hardness, which can be measured according to ASTM D 3363.
• An evaluation of the solvent resistance can be made in accordance with EN ISO 2812-3: 2007. It is noteworthy that the surface of the molded article obtained by coating the film with the coating agent according to the invention and finally curing by UV radiation itself has good resistance to the solvent acetone, which is otherwise very harmful for polycarbonate surfaces.
• the molding according to the invention is obtainable by means of film insert molding, wherein the film insert molding comprises filling a 3D-shaped film comprising the protective layer with the melt of a thermoplastic polymer on the protective layer facing away from the film.
• Film insert molding in the context of the present invention is a process in which the film is coated with the coating agent, the film is thereafter thermally deformed three-dimensionally, for example, and then the film with the thermoplastic polymer on the film side facing away from behind or injected.
• the coating may already include a drying process.
• the coating on the surface of the film is preferably hardened by means of actinic radiation, preferably UV radiation, before the back-coating process.
• thermoplastics such as polycarbonate, polyacrylate or poly (meth) acrylate, polysulfones, polyesters, thermoplastic polyurethane and polystyrene and their copolymers and blends (blends) are used.
• thermoplastics are, for example, polyacrylates, poly (meth) acrylates (eg PMMA, eg Plexiglas® from Röhm), cycloolefin copolymers (COC, eg Topas® from Ticona, Zenoex® from Nippon Zeon or Apel From Japan Synthetic Rubber), polysulfones (Ultrason® from BASF or Udel® from Solvay), polyesters, such as PET or PEN, polycarbonate (PC), polycarbonate / polyester blends, e.g. PC / PET, polycarbonate / polycyclohexylmethanol cyclohexanedicarboxylate (PCCD, Xylecs® from GE), polycarbonate / PBT and mixtures thereof.
• PC polycarbonate
• PCCD polycyclohexylmethanol cyclohexanedicarboxylate
• PCCD Xylecs® from GE
• the film of the molding according to the invention comprises polycarbonate or copolycarbonate.
• polycarbonate in the context of the present invention is also used as a thermoplastic polymer for injection-molding or filling the 3D-formed film coated with the protective layer.
• the thermoplastic polymer thus comprises polycarbonate.
• Polycarbonates and polycarbonate preparations suitable for the invention and also polycarbonate films are obtainable, for example, under the trade names Makrolon®, Bayblend® and Makroblend® (Bayer MaterialScience AG).
• Suitable polycarbonates for the preparation of the polycarbonate compositions according to the invention are all known polycarbonates. These are homopolycarbonates, copolycarbonates and thermoplastic polyestercarbonates.
• the suitable polycarbonates preferably have average molecular weights M w from 18,000 to 40,000, preferably from 26,000 to 36,000 and especially from 28,000 to 35,000, determined by measuring the relative solution viscosity in dichloromethane or mixtures of equal amounts by weight phenol / o-dichlorobenzene calibrated by light scattering.
• the preparation of the polycarbonates is preferably carried out by the interfacial process or the melt transesterification process, which are described in various ways in the literature.
• interfacial process is an example H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 p. 33 et seq., On Polymer Reviews, Vol. 10 , " Condensation Polymers by Interfacial and Solution Methods ", Paul W. Morgan, Interscience Publishers, New York 1965, Chapter VIII, p. 325 , on Dres. U. Grigo, K. Kircher and P.
• the polycarbonates can be obtained from reactions of bisphenol compounds with carbonic acid compounds, in particular phosgene or in the melt transesterification process diphenyl carbonate or dimethyl carbonate.
• carbonic acid compounds in particular phosgene or in the melt transesterification process diphenyl carbonate or dimethyl carbonate.
• homopolycarbonates based on bisphenol A and copolycarbonates based on the monomers bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane are particularly preferred.
• Other bisphenol compounds that can be used for the polycarbonate synthesis are disclosed, inter alia, in WO-A 2008037364 .
• WO-A 2002026862 WO-A 2005113639
• the polycarbonates may be linear or branched. It is also possible to use mixtures of branched and unbranched polycarbonates.
• Suitable branching agents for polycarbonates are known from the literature and described for example in the patents US-B 4 185 009 . DE-A 25 00 092 . DE-A 42 40 313 . DE-A 19 943 642 . US Pat. No. 5,367,044 as well as in literature cited herein.
• the polycarbonates used can also be intrinsically branched, in which case no branching agent is added during the polycarbonate production.
• An example of intrinsic branching are so-called frieze structures, as used for melt polycarbonates in the EP-A 1 506 249 are disclosed.
• chain terminators can be used in polycarbonate production.
• the chain terminators used are preferably phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof.
• the plastic composition (s) of the film or of the thermoplastic polymer of the 3D molded article may additionally contain additives such as UV absorbers, IR absorbers and other customary processing aids, in particular mold release agents and flow agents, as well as the usual stabilizers, in particular heat stabilizers and antistatic agents, pigments , Colorants and optical brighteners. In each layer different additives or concentrations of additives may be present.
• the coating composition according to claim 1 is a further subject of the present invention.
• This comprises (a) at least one thermoplastic polymer having an average molecular weight of at least 100,000 g / mol in a content of 30 wt .-% of the solid content of the coating agent; (b) at least 30% by weight of a UV-curable reactive diluent; (c) ⁇ 0.1 to ⁇ 10 parts by weight of at least one photoinitiator; and (d) at least one organic solvent, wherein the proportion of ethylenically unsaturated groups is at least 3 moles per kg of the solids content of the coating agent.
• thermoplastic polymers polymethyl methacrylate (PMMA), polyesters of various types (eg PET, PEN, PBTP and UP), other plastics such as rigid PVC, cellulose esters (such as CA, CAB, CP), polystyrene (PS) and copolymers (SAN , SB and MBS), polyacrylonitrile (PAN), ABS plastics, acrylonitrile methyl methacrylate (AMMA), acrylonitrile-styrene-acrylic ester (ASA), polyurethane (PUR), polyethylene (PE, PE-HD, -LD, -LLD, -C ), Polypropylene (PP), polyamide (PA), polycarbonate (PC) or polyethersulfone (PES) / (abbreviated to DIN 7728T1).
• PMMA polymethyl methacrylate
• polyesters of various types eg PET, PEN, PBTP and UP
• other plastics such as rigid PVC, cellulose esters (such as CA, CA
• thermoplastic polymers having a molecular weight Mw of at least 100,000 g / mol advantageously contribute to a sufficient blocking resistance of the dried coating on the one hand and, on the other hand, to scratch resistance and solvent resistance of the surface coating hardened by UV radiation, for example.
• thermoplastic polymers having a molecular weight Mw of at least 150,000 g / mol, more preferably having a molecular weight Mw of at least 200,000 g / mol are preferred.
• the Vicaterweichungstemperaturen VET (ISO 306) are preferably in the range of at least 90 ° C, preferably at least 95 ° C, more preferably at least 100 ° C.
• thermoplastic polymer is polymethylmethacrylate.
• Polymethyl methacrylate is understood as meaning polymethyl methacrylate homopolymer and copolymers based on methyl methacrylate with the methyl methacrylate content of more than 70% by weight, as described, for example, under the trade names Degalan® , Degacryl® , Plexyglas® , Acrylite® (Evonik ) Altuglas, Oroglas (Fa. Arkema), Elvacite ®, Colacryl ®, Lucite ® (Fa. Lucite) and, inter alia, under the names of acrylic glass, Conacryl, Deglas, deacon, Friacryl, Hesaglas, Limacryl, PerClax and vitroflex are known.
• the thermoplastic polymer comprises (a) PMMA homopolymers and copolymers of 70 wt .-% to 99.5 wt .-% of methyl methacrylate and 0.5 wt .-% to 30 wt .-% of methyl acrylate. Particularly preferred are PMMA homopolymers and copolymers of 90 wt .-% to 99.5 wt .-% of methyl methacrylate and 0.5 wt .-% to 10 wt .-% of methyl acrylate.
• Vicat softening temperatures VET are in a preferred embodiment in the range of at least 90 ° C, preferably from 100 ° C to 115 ° C.
• PMMA homopolymers and copolymers having a molecular weight Mw of at least 100,000 g / mol contribute particularly advantageously to the scratch resistance and solvent resistance of the surface coating according to the invention.
• the invention uses PMMA homopolymers and copolymers having a molecular weight Mw of at least 100,000 g / mol, more preferably having a molecular weight Mw of at least 150,000 g / mol, very particularly preferably having a molecular weight Mw of at least 200,000 g / mol.
• the determination of the molecular weight Mw is carried out by gel permeation chromatography (see, for example, US Pat. HF Mark et al., Encyclopedia of Polymer Science and Engineering, 2nd. Edition, Vol. 10, pages 1 ff., J. Wiley, 1989 ).
• the proportion of the thermoplastic polymer is at least 30 wt .-%, more preferably at least 40 wt .-% and most preferably 45 wt .-% in the solid content of the coating composition.
• bifunctional, trifunctional, tetrafunctional, pentafunctional or hexafunctional acrylic and / or methacrylic monomers can be used as reactive diluents. These are preferably ester functions, in particular acrylic ester functions.
• Suitable polyfunctional acrylic and / or methacrylic acid esters are derived from aliphatic polyhydroxy compounds having at least 2, preferably at least 3 and more preferably at least 4 hydroxy groups and preferably from 2 to 12 carbon atoms.
• aliphatic polyhydroxy compounds examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tetramethylolethane and sorbitan.
• esters which are suitable as reactive diluents according to the invention are glycol diacrylate and dimethacrylate, butanediol diacrylate or dimethacrylate, dimethylolpropane diacrylate or dimethacrylate, diethylene glycol diacrylate or dimethacrylate, divinylbenzene, trimethylolpropane triacrylate or trimethacrylate, glycerol triacrylate or trimethacrylate, pentaerythritol tetraacrylate or tetramethacrylate, dipentaerythritol penta / hexaacrylate (DPHA), 1,2,3,4-butanetetraetetraacrylate or tetramethacrylate, tetramethylolethane tetraacrylate or tetramethacrylate, 2,2-dihydroxypropanediol-1,3-tetraacrylate or tetramethacrylate, diurethane dim
• alkoxylated di-, tri-, tetra-, penta- and hexacrylates or -methacrylates examples are alkoxylated, preferably ethoxylated methanediol diacrylate, methanediol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 2-butyl-2-ethyl-1,3- Propandioldimethacrylate, trimethylolpropane diacrylate or trimethylolpropane dimethacrylate.
• alkoxylated triacrylates or methacrylates are alkoxylated, preferably ethoxylated pentaerythritol triacrylate, pentaerythritol trimethacrylate, glycerol triacrylate, glycerol trimethacrylate, 1,2,4-butanetriol triacrylate, 1,2,4-butanetriol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecane, Tricyclodecandimethanoldimethacrylat, ditrimethylolpropane tetraacrylate or Ditrimethylolpropantetramethacrylat.
• alkoxylated tetra-, penta- or hexaacrylates are alkoxylated, preferably ethoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate dipentaerythritol hexaacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol penta methacrylate or dipentaerythritol hexamethacrylate.
• alkoxylated diacrylates or methacrylates triacrylates or methacrylates, tetraacrylates or methacrylates, pentaacrylates or methacrylates and / or alkoxylated hexaacrylates or methacrylates of component b)
• all acrylate groups or methacrylate groups or only a part of the acrylate groups or methacrylate groups in the respective monomer be bound via alkylene oxide to the corresponding radical. It is also possible to use any desired mixtures of such fully or partially alkoxylated di-, tri-, tetra-, penta- or hexaacrylates or -methacrylates.
• the acrylate or methacrylate group (s) are bonded to the aliphatic, cycloaliphatic or aromatic radical of the monomer via a plurality of successive alkylene oxide groups, preferably ethylene oxide groups.
• the average number of alkylene oxide or ethylene oxide groups in the monomer is indicated by the degree of alkoxylation or degree of ethoxylation.
• the degree of alkoxylation or degree of ethoxylation may preferably be from 2 to 25, with particular preference being given to degrees of alkoxylation or degrees of ethoxylation of from 2 to 15, very particularly preferably from 3 to 9.
• oligomers which belong to the class of aliphatic urethane acrylates as reactive diluents or as component b) of the coating composition according to the invention or the polyester acrylates or polyacrylacrylates.
• Their use as paint binders is known and is known in Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Vol. 2, 1991, SITA Technology, London (PKT: Oldring (Ed.) At p.73-123 (Urethane Acrylates) and p.123-135 respectively (Polyester acrylates ).
• aliphatic urethane acrylates such as Ebecryl® 4858, Ebecryl® 284, Ebecryl® 265, Ebecryl® 264, Ebecryl® 8465, Ebecryl® 8402 (each manufacturer Cytec Surface Specialties), Craynor® 925 from Cray Valley , Viaktin® 6160 from Vianova Resin, Desmolux VP LS 2265 from Bayer MaterialScience AG, Photomer 6891 from Cognis or aliphatic urethane acrylates also dissolved in reactive diluents such as Laromer® 8987 (70% in hexanediol diacrylate) from BASF AG, Desmolux U 680 H (80%).
• reactive diluents such as Laromer® 8987 (70% in hexanediol diacrylate) from BASF AG, Desmolux U 680 H (80%).
• the reactive diluent (b) comprises alkoxylated diacrylates and / or dimethacrylates, alkoxylated triacrylates and / or trimethacrylates, alkoxylated tetraacrylates and / or tetramethacrylates, alkoxylated pentaacrylates and / or pentamethacrylates, alkoxylated hexaacrylates and / or hexamethacrylates, aliphatic urethane acrylates, polyester acrylates, polyacrylacrylates and mixtures from that.
• the proportion of the multifunctional monomers in such a mixture is preferably at least 20 wt .-%.
• the reactive diluent (b) of the coating composition according to the invention comprises dipentaerythritol penta / hexaacrylate.
• the reactive diluent is an essential part of the coating composition according to the invention and of the coating according to the invention.
• the proportion of the reactive diluent overall is at least 30 wt .-%, more preferably at least 40 wt .-%, most preferably at least 45 wt .-% in the solid content of the coating composition.
• the coating composition of the invention contains a content of ethylenically unsaturated groups of at least 3.0 moles per kg solids content of the coating composition, preferably at least 3.5 moles per kg, more preferably at least 4.0 moles per kg solids content of the coating composition.
• the term of the at least one photoinitiator of the coating composition of the invention comprises the common, known to those skilled, commercially available compounds such.
• UV photoinitiators used are BASF's IRGACURE® grades such as IRGACURE® 184, IRGACURE® 500, IRGACURE® 1173, IRGACURE®2959, IRGACURE® 745, IRGACURE® 651, IRGACURE® 369, IRGACURE® 907 , IRGACURE® 1000, IRGACURE® 1300, IRGACURE® 819, IRGACURE® 819DW, IRGACURE® 2022, IRGACURE® 2100, IRGACURE® 784, IRGACURE® 250, and BASF's DAROCUR® grades, such as the DAROCUR® grades MBF, DAROCUR® 1173, DAROCUR® TPO, DAROCUR® 4265 used. Et al the other UV photoinitiators are used, e.g. Esacure One (Lamberti).
• Photoinitiators are included in the coating composition in the range of ⁇ 0.1 to ⁇ 10 parts by weight of the solids content of the coating composition.
• the coating composition contains one or more organic solvents beyond the 100 parts by weight of components 1) to 3).
• organic solvents may be selected, for example, from the group containing aromatic solvents, e.g. Xylene or toluene, ketones, e.g. Acetone, 2-butanone, methyl isobutyl ketone, diacetone alcohol, alcohols, e.g. Methanol, ethanol, i-propanol, butanol, 1-methoxy-2-propanol, ethers, e.g. 1,4-dioxane, ethylene glycol n-propyl ether, or esters, e.g. Ethyl acetate, butyl acetate, 1-methoxy-2-propyl acetate or mixtures containing these solvents.
• aromatic solvents e.g. Xylene or toluene
• ketones e.g. Acetone, 2-butanone, methyl isobutyl ketone
• ethanol i-propanol, butanol, ethyl acetate, butyl acetate, 2-methoxypropyl alcohol, diacetone alcohol, xylene or toluene.
• Particularly preferred are i-propanol, butanol, ethyl acetate, butyl acetate, 1-methoxy-2-propanol, diacetone alcohol and their mixtures.
• Very particular preference is given to 1-methoxy-2-propanol and diacetone alcohol, particular preference to 1-methoxy-2-propanol.
• the coating composition preferably contains in addition to the 100 parts by weight of the components 1) to 3) 0 to 900 parts by weight, more preferably 100 to 850 parts by weight, most preferably 200 to 800 parts by weight of at least one organic Solvent (component 4).
• the coating composition may optionally contain one or more additional coating additives in addition to the 100 parts by weight of components 1) to 3).
• additional coating additives may, for example, be selected from the group comprising stabilizers, leveling agents, surface additives, pigments, dyes, inorganic nanoparticles, adhesion promoters, UV absorbers, IR absorbers, preferably from the group comprising stabilizers, leveling agents, surface additives and inorganic nanoparticles.
• the paint composition preferably contains in addition to the 100 parts by weight of the components 1) to 3) 0 to 35 parts by weight, particularly preferably 0 to 30 parts by weight, most preferably 0.1 to 20 parts by weight at least another paint additive.
• the total amount of all coating additives contained in the coating composition is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, most preferably 0.1 to 10 parts by weight.
• composition of the coating agent may include inorganic nanoparticles for increasing mechanical resistance, such as e.g. Scratch resistance and / or pencil hardness included.
• Suitable nanoparticles are inorganic oxides, mixed oxides, hydroxides, sulfates, carbonates, carbides, borides and nitrides of elements of the II to IV main group and / or elements of the I to VIII transition group of the periodic table, including the lanthanides.
• Preferred nanoparticles are silica, alumina, ceria, zirconia, niobium oxide, zinc oxide or titanium oxide nanoparticles, particularly preferred are silica nanoparticles.
• the particles used preferably have mean particle sizes (measured by means of dynamic light scattering in dispersion determined as the Z mean) of less than 200 nm, preferably from 5 to 100 nm, particularly preferably from 5 to 50 nm.
• mean particle sizes measured by means of dynamic light scattering in dispersion determined as the Z mean
• the coating composition can be easily prepared by first completely dissolving the polymer in the solvent at room temperature or at elevated temperatures, and then adding the other compulsory and optionally optional components to the room temperature cooled solution either in the absence of solvent (s) and mixed together by stirring or in the presence of solvent (s) for example, in the solvent (s) and mixed together by stirring.
• the photoinitiator is first dissolved in the solvent (s) and then the further components are added.
• subsequent purification by filtration, preferably by means of fine filtration.
• the coating of the film with the coating agent can be carried out by the conventional methods of coating films with liquid coating compositions, such as by knife coating, spraying, pouring, flooding, dipping, spraying, rolling or spin-coating.
• the flood process can be done manually with hose or suitable coating head or automatically in the run on flood painting robot and possibly slot nozzles. Preference is given to a application of the coating agent via a roll to roll transfer.
• the surface of the film to be coated can be pretreated by cleaning or activation.
• the drying follows the application of the coating agent to the film. For this purpose, in particular with increased temperatures in ovens and with moving and possibly also dehumidified air such as in convection ovens or by jet dryers and heat radiation such as IR and / or NIR worked. Furthermore, microwaves can be used. It is possible and advantageous to combine several of these drying methods.
• the drying of the coating in step (II) preferably comprises flash-off at room temperature and / or elevated temperature, such as preferably at 20-200 ° C., more preferably at 40-120 ° C. After the coating has dried, it is block-resistant, so that the coated substrate, in particular the coated film, can be printed, printed, and / or thermally deformed. In particular, the deformation is preferred because even here by the deformation of a coated film, the shape of a film insert molding process for producing a three-dimensional plastic part can be specified.
• the conditions for the drying are chosen so that no polymerization (crosslinking) of the acrylate or methacrylate groups is triggered by the increased temperature and / or the heat radiation, since this can affect the deformability.
• the maximum temperature reached is expediently to be chosen so low that the film does not deform uncontrollably.
• the coated film After the drying / curing step, the coated film, optionally after lamination with a protective film on the coating, can be rolled up. Rolling up can be done without sticking the coating to the back side of the substrate film or the laminating film. But it is also possible to cut the coated film and feed the blanks individually or as a stack of further processing.
• curing with actinic radiation is meant the free radical polymerization of ethylenically unsaturated carbon-carbon double bonds by means of initiator radicals which are released by irradiation with actinic radiation, for example from the photoinitiators described above.
• the radiation curing is preferably carried out by the action of high-energy radiation, ie UV radiation or daylight, for example light of wavelength from ⁇ 200 nm to ⁇ 750 nm, or by irradiation with high-energy electrons (electron radiation, for example from ⁇ 90 keV to ⁇ 300 keV).
• high-energy radiation ie UV radiation or daylight
• high-energy electrons electron radiation, for example from ⁇ 90 keV to ⁇ 300 keV.
• medium or high pressure mercury vapor lamps are used as radiation sources for light or UV light, wherein the mercury vapor may be modified by doping with other elements such as gallium or iron.
• Lasers, pulsed lamps (known as UV flash emitters), halogen lamps or excimer emitters can also be used.
• the radiators can be installed immovable, so that the material to be irradiated is moved past the radiation source by means of a mechanical device, or the radiators can be movable, and the material to be irradiated does not change its location during curing.
• the radiation dose for UV curing which is usually sufficient for crosslinking, is in the range of ⁇ 80 mJ / cm 2 to ⁇ 5000 mJ / cm 2 .
• the actinic radiation is therefore light in the range of UV light.
• the irradiation may optionally also be carried out in the absence of oxygen, for example under an inert gas atmosphere or oxygen-reduced atmosphere.
• inert gases are preferably nitrogen, carbon dioxide, noble gases or combustion gases.
• the irradiation can be carried out by covering the coating with media transparent to the radiation. Examples include plastic films, glass or liquids such as water.
• the type and concentration of the optionally used initiator can be varied or optimized in a manner known to the person skilled in the art or by preliminary preliminary experiments.
• unirradiated areas should be avoided.
• the irradiation conditions such that the thermal load on the film does not become too great.
• thin films as well as films of materials with low glass transition temperature can tend to uncontrolled deformation when the irradiation exceeds a certain temperature.
• by reducing the corresponding radiation dose of the uncontrolled deformation can be counteracted. It should be noted, however, that a certain dose and intensity of irradiation are necessary for as complete a polymerization as possible. It is particularly advantageous in these cases, under To harden in inert or oxygen-reduced conditions, since reducing the oxygen content in the atmosphere above the coating, the required dose for curing decreases.
• mercury radiators are particularly preferably used in fixed installations.
• Photoinitiators are then used in concentrations of from ⁇ 0.1% by weight to ⁇ 10% by weight, particularly preferably from ⁇ 0.2% by weight to ⁇ 3.0% by weight, based on the solids of the coating.
• a dose of ⁇ 80 mJ / cm 2 to ⁇ 5000 mJ / cm 2 is preferably used.
• step (V) takes place by means of extrusion or injection molding, preferably with polycarbonate melt.
• the 3D molded parts according to the invention are suitable for use in products in the fields of architecture, automotive, rail vehicle, aircraft, the manufacture of visors of Protective helmets and the production of electronic products.
• Another object of the present invention therefore relates to a product comprising the inventive 3D molded part.
• the product is a transparent glazing, cover or viewing window from the fields of architecture, automotive, rail vehicle, aircraft, the manufacture of visors of protective helmets and the manufacture of electronic products or a transparent or non-transparent part of an interior or exterior of Automobiles, such as a dashboard, a pillar cover, a sunroof, or a bumper.
• Another object relates to the use of the inventive 3D molded body as graphicurverscheibung, Automobilverscheibung, SchienenINDverscheibung, Wasserververibbling, Klicetverscheibung, Karosserieabdeckteil, Windshield, helmet visor, electronics housing part, mecanicaustattungsteil of automobiles, rail vehicles, watercraft or aircraft.
• the layer thickness of the coatings was measured by observing the cut edge in an optical microscope of the type Axioplan manufacturer Zeiss. Method - reflected light, bright field, magnification 500x.
• the pencil hardness was measured according to ASTM D 3363 using an Elcometer 3086 Scratch boy (Elcometer Instruments GmbH, Aalen, Germany) at a loading of 500 g unless otherwise specified.
• the steel wool scratching is determined by a steel wool no. 00 (Oskar Weil GmbH Rakso, Lahr, Germany) is glued to the flat end of a 500 g locksmith hammer, the area of the hammer is 2.5 cm x 2.5 cm, ie about 6.25 cm 2 .
• the hammer is placed without additional pressure on the surface to be tested, so that a defined load of about 560 g is achieved.
• the hammer is then moved 10 times in double strokes back and forth. Subsequently, the contaminated surface is cleaned with a soft cloth of fabric residues and paint particles. Scratch is characterized by haze and gloss values measured across the scratch direction with a Micro HAZE plus (20 ° gloss and Haze; Byk-Gardner GmbH, Geretsried, Germany). The measurement takes place before and after scratching.
• the solvent resistance of the coatings was usually tested with isopropanol, xylene, 1-methoxy-2-propyl acetate, ethyl acetate, acetone in technical grade.
• the solvents were applied to the coating with a soaked cotton swab and protected from evaporation by capping. Unless otherwise stated, an exposure time of 60 minutes was maintained at about 23 ° C. After the end of the exposure time, the cotton ball is removed and the test surface wiped clean with a soft cloth. The matching takes place immediately visually and after slight scratching with the fingernail.
• the toughness rating was based on a drop test based on the DIN EN ISO 6603-1 standard. Analogous to the standard, a puncture test with varied falling energy is carried out, whereby this is done by varying the drop height with a constant falling mass. As a measure of the fall energy, the impact velocity is measured directly by means of a light barrier and specified as a variation parameter.
• the critical impact velocity was varied within a suitable range and the fracture behavior (tough / brittle) associated with a selected velocity was determined.
• the type of fracture was determined on the basis of the fracture pattern of the beaten test specimens.
• a fracture fracture is defined as both plastic deformation without cracking (according to standard) and (deviating from the standard) puncturing the test specimen if it is in one Piece remains - as a brittle fracture the breaking of the sample into two or more pieces is considered.
• the measured critical impact velocities are between 2 - 2.5 m / s and 13 m / s. Samples that show a brittle fracture even at minimum impact velocity are generally judged to be brittle, the critical impact velocity is given as " ⁇ 2.0 m / s".
• Each multilayer structure is thus characterized by the critical impact velocity and can thus be compared and evaluated with other systems.
• the thickness of the specimens influences the deformation and fracture behavior under mechanical stress.
• the absolute measured values show a dependency on the sample thickness and can not be compared directly with one another for differently sized test specimens. Therefore, within the scope of the present invention, samples of 4 mm thickness have been used whose performance can be compared with one another and whose thickness is in a typical size for many applications.
• the relative differences in the toughness of the various systems - in terms of the position of the toughened / brittle transition or the critical impact velocity - can also be transferred to other sample thicknesses.
• tensile zone here means the sample side, which is opposite to the impactor and is therefore subjected to tensile stress in the penetration test.
• Pressure zone the sample area under the impactor on the impact side, where mostly a pressure load occurs.
• Example 1 Preparation of a coating agent
• the coating composition was stirred for a further 3 hours at room temperature and under the influence of direct light, filled up, and then allowed to stand for 1 day.
• the yield was 250 g, the viscosity (23 ° C) about 9000 mPas and the solids content 19 wt .-%.
• the double bond density in the solids content of the coating composition was calculated to be about 5.1 mol / kg.
• a coating composition was prepared from Degalan M345 (PMMA; Fa. Evonik; M w 180,000) analogously to Example 1.
• the yield was 275 g, the solids content 19 wt .-%.
• the double bond density in the solids content of the coating composition was calculated to be about 5.1 mol / kg.
• Comparative Example 1 Preparation of comparative coating agent
• a coating composition was prepared from Degalan M825 (PMMA; Fa. Evonik; M w 80,000) analogously to Example 1.
• the yield was 280 g, the solids content 19 wt .-%.
• the double bond density in the solids content of the coating composition was calculated to be about 5.1 mol / kg.
• Example 1 The coating compositions of Examples 1 and 2 and Comparative Example 1 were each applied by means of a slot caster of the company "TSE Troller AG” on a carrier film Makrofol DE 1-1 (Bayer MaterialScience AG, Leverkusen, Germany) in.
• the layer thickness of the carrier film was 250 .mu.m, the layer thicknesses of the coatings are shown in Tables 1 to 3.
• the coating was roll on roll, that is, the polycarbonate film was rolled in the coating system.
• the film was passed through one of the above application units and charged with the coating solution. Thereafter, the film with the wet coating was passed through the dryer. After exiting the dryer, the now dry coating was provided with a laminating film to protect it from dirt and scratching. Thereafter, the film was rolled up again.
• the coated film can be initially cured with UV lamp after exit from the dryer and then provided with a laminating film.
• Example 3 The coated side of the non-UV cured films produced in Example 3 is covered with a type GH-X 173 A laminating film (Bischof + Klein, Lengerich, Germany) and beaten for 1 h at about 23 ° C. with an aluminum plate 4.5 x 4.5 cm 2 and a weight of 2 kg applied. After that hour, the weight and liner are removed and the surface of the coating is visually inspected for changes.
• a type GH-X 173 A laminating film (Bischof + Klein, Lengerich, Germany) and beaten for 1 h at about 23 ° C. with an aluminum plate 4.5 x 4.5 cm 2 and a weight of 2 kg applied. After that hour, the weight and liner are removed and the surface of the coating is visually inspected for changes.
• the HPF deformation experiments were carried out on a SAMK 360 system from Niebling (DE).
• the tool was electrically heated to 100 ° C.
• the film heating was carried out by means of IR radiators at 240-260-280 ° C.
• the heating time was 16 seconds. It was reached a film temperature of about 170 ° C.
• the deformation took place at a deformation pressure of 100 bar.
• the deformation tool was a heater / vent panel (HL panel).
• the foil sheet was fixed in position on a pallet.
• the pallet went through the deformation station in the heating zone and stayed there for the set time (16 s).
• the film was heated so that the film briefly experienced a temperature above the softening point, the core of the film was about 10-20 ° C colder. As a result, the film was relatively stable when it was moved into the deformation station.
• the film was fixed by moving the tool over the actual tool, at the same time the film is shaped by means of gas pressure over the tool.
• the pressure holding time of 7 seconds ensured that the film molded the tool accurately.
• the gas pressure was relieved again.
• the film was then removed from the pallet and could now be cured with UV light.
• the UV curing of the coating according to the invention was carried out using a high-pressure mercury vapor lamp of the evo 7 dr type (ssr engineering GmbH, Lippstadt, Germany).
• the system was equipped with dichroic reflectors and quartz discs and has a specific power of 160 W / cm.
• a UV dose of 2.0 J / cm 2 and an intensity of 1.4 W / cm 2 was applied.
• the surface temperature should reach> 60 ° C.
• the UV dose was determined using a Lightbug ILT 490 (International Light Technologies Inc., Peabody MA, USA).
• the surface temperature data were determined using RS temperature test strips (order number 285-936, RS Components GmbH, Bad Hersfeld, Germany).
• Table 1 shows that an improvement in pencil hardness and scratch resistance could be achieved by the coating according to the invention.
• the coating resulted in a very good solvent resistance of the films.
• the solvent resistance of the coated films to acetone.
• Acetone the most aggressive solvent for coated polycarbonate, such as that available under the trademark Makrofol (Bayer), has almost no effect on the final coating according to the invention within a contact time of 1 hour (characteristic value ⁇ 1, scoring 0 to 5). This means that the solvent resistance for this coating is at the level of the best (but non-deformable) hardcoat coatings of the prior art.
• samples were produced by the invention according to the invention coated flat polycarbonate films of Makrofol DE 1-1 (250 .mu.m) according to the numbers 1 to 6 in A5-format from the uncoated side with polycarbonate were back-injected.
• the back molding was carried out on an injection molding machine of the company Arburg type Allrounder 560 C 2000-675 / 350. The machine has a screw diameter of 45 mm.
• the Makrolon was back-injected with a melt temperature of 280 ° C.
• the filling time for filling the tool was 2 sec.
• the mold temperature was varied. Good results could be achieved with a mold temperature of 80 ° C and 100 ° C. A negative effect visually did not exist in this regard.
• the hold time was 12 seconds and the cooling time was 20 seconds.
• the polycarbonate used was Makrolon AL 2647 (Bayer MaterialScience AG).
• the layer thickness of the applied polycarbonate was 4 mm. From the thus obtained polycarbonate film laminates, 60 ⁇ 60 mm 2 test pieces were sawn.
• the plate penetration test was carried out in accordance with DIN EN ISO 6603-1 with 13 kg drop weight at different impact speeds with an instrumented case manufactured by RoellAmsler (IFW 420) at -30 ° C. Mandrel diameter 20mm, support diameter 40 mm. The impact velocity was varied to determine the tough / brittle transition.
• the type of fracture was determined on the basis of the fracture pattern of the beaten specimens.
• the fracture fracture involved both plastic deformation without cracking (standard) and (deviating from the standard) puncturing the specimen, if it was in one Piece remained.
• As a brittle fracture the breakage of the sample was evaluated in two or more parts.
• test specimens with the coating according to the invention in a thickness of 5 .mu.m also show the same high level of viscosity.
• the brittle fracture can indeed be caused, but the critical speeds remain for the coatings up to 17 microns above the level of 2.0 m / s. Only at the coating of 25 microns, the critical speed falls below this limit, which is set as the lower limit for performance-sufficient ductile behavior.
• plastic parts produced by the process described here regardless of the direction of impact have a low temperature toughness sufficient for typical applications, if the layer thickness of the coating of the film does not exceed 20 microns.
• the moldings according to the invention thus have an excellent direction-independent impact strength even at low temperatures with a simultaneous special scratch resistance and solvent resistance of the surface.
• This combination of properties makes them excellently suitable for the production of plastic parts for automobiles, aircraft, rail vehicles, electronics, interior and exterior architecture.
• the molded parts according to the invention are suitable for use as transparent panes in the architectural, automotive, aircraft and rail vehicle sectors.

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• 2014
  • 2014-06-11 EP EP14732117.8A patent/EP3008144B1/de not_active Not-in-force
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